Process for combined hydrodesulfurization and hydrocracking of heavy hydrocarbons

Abstract

The present invention relates to a process for combined hydrodesulfurization and hydrocracking of a heavy hydrocarbon feed comprising contacting the hydrocarbon feed in the presence of hydrogen with a catalyst comprising a mixture of a solid acid catalyst and a hydrodesulfurization catalyst.

The invention claimed is: 
     
       1. A process for combined hydrodesulfurization and hydrocracking of a heavy hydrocarbon feed comprising:
 contacting said heavy hydrocarbon feed in the presence of hydrogen at process conditions comprising a temperature of 400-455° C. and a pressure of 2500-4500 kPa, with a catalyst comprising a mixture of a solid acid catalyst and a hydrodesulfurization catalyst, wherein sulfur is at least partially removed from the heavy hydrocarbon feed; 
 a mono-aromatic yield of about 19% to about 52%; 
 a sulfur component reduction of greater than or equal to about 96%; 
 a di and tri-aromatic ring opening conversion of about 17% to about 38%; 
 a molar selectivity to mono-aromatics of about 64% to about 94%; 
 wherein said hydrodesulfurization catalyst comprises 1-30 wt-% of an element selected from Group 6 of the Periodic Table of Elements based on the total weight of the hydrodesulfurization catalyst, and 0.1-10 wt-% of an element selected from Groups 9 and 10 of the Periodic Table of Elements based on the total weight of the hydrodesulfurization catalyst and a solid catalyst support, and 
 wherein said solid acid catalyst comprises an aluminosilicate zeolite Y having a SiO 2 /Al 2 O 3  molar ratio of 60-100. 
 
     
     
       2. The process according to  claim 1 , wherein the element selected from Groups 9 and 10 of the Periodic Table of Elements is Co and/or Ni. 
     
     
       3. The process according to  claim 1 , wherein the element in the hydrodesulfurization catalyst is in sulfide form. 
     
     
       4. The process according to  claim 1 , wherein the hydrodesulfurization catalyst comprises one or more selected from the group consisting of CoMoS 2 , NiMoS 2 , NiWS 2  and CoWS 2 . 
     
     
       5. The process according to  claim 1 , wherein the solid acid catalyst comprises aluminosilicate zeolite having a 12-ring structure. 
     
     
       6. The process according to  claim 5 , wherein the aluminosilicate zeolite has super cages having a size of 12-14 Å. 
     
     
       7. The process according to  claim 1 , wherein the process conditions comprise a pressure of 2700-4000 kPa. 
     
     
       8. The process according to  claim 1 , wherein the process conditions further comprise a Weight Hourly Space Velocity (WHSV) of 0.05-5 h −1 . 
     
     
       9. The process according to  claim 1 , wherein the heavy hydrocarbon feed comprises at least 30 wt-% polyaromatics. 
     
     
       10. The process according to  claim 1 , wherein the heavy hydrocarbon feed comprises at least 100 wppm sulfur. 
     
     
       11. The process according to  claim 1 , wherein the heavy hydrocarbon feed comprises one or more selected from the group consisting of heavy cycle oil, light cycle oil, carbon black oil, cracked distillate and pyoil. 
     
     
       12. The process according to  claim 1 ,
 wherein the pressure is 2800-3500 kPa, 
 wherein the WHSV of 0.1-1.5 h −1 , and 
 wherein the heavy hydrocarbon feed comprises at least 50 wt-% polyaromatics. 
 
     
     
       13. The process according to  claim 12 , wherein the heavy hydrocarbon feed comprises at least 5000 wppm sulfur. 
     
     
       14. A process for combined hydrodesulfurization and hydrocracking of a heavy hydrocarbon feed comprising:
 contacting said heavy hydrocarbon feed in the presence of hydrogen at process conditions comprising a temperature of 400-455° C., a Weight Hourly Space Velocity (WHSV) of 0.05-5 h −1 , and a pressure of 2800-3500 kPa, with a catalyst comprising a mixture of a solid acid catalyst and a hydrodesulfurization catalyst, wherein sulfur is at least partially removed from the heavy hydrocarbon feed; 
 a mono-aromatic yield of about 19% to about 52%; 
 a sulfur component reduction of greater than or equal to about 96%; 
 a di- and tri-aromatic ring opening conversion of about 17% to about 38%; 
 a molar selectivity to mono-aromatics of about 64% to about 94%; 
 wherein the heavy hydrocarbon feed comprises at least 30 wt-% polyaromatics, 
 wherein the solid acid catalyst comprises aluminosilicate zeolite having a 12-ring structure and having super cages having a size of 12-14 Å, 
 wherein said hydrodesulfurization catalyst comprises 1-30 wt-% of Co and/or Ni based on the total weight of the hydrodesulfurization catalyst, and 0.1-10 wt-% of an element selected from Groups 9 and 10 of the Periodic Table of Elements based on the total weight of the hydrodesulfurization catalyst and a solid catalyst support, and 
 wherein said solid acid catalyst comprises an aluminosilicate zeolite Y having a SiO 2 /Al 2 O 3  molar ratio of 60-100. 
 
     
     
       15. The process according to  claim 1 , wherein the hydrodesulfurization catalyst comprises one or more selected from the group consisting of CoMoS 2 , NiMoS 2 , NiWS 2  and CoWS 2 . 
     
     
       16. The process according to  claim 1 , wherein the WHSV is 0.1-1.5 h −1 . 
     
     
       17. The process according to  claim 1 , wherein the heavy hydrocarbon feed comprises at least 50 wt-% polyaromatics, and comprises at least 1000 wppm sulfur.